TWI482882B - Surface treatment of copper foil and the use of its laminated board - Google Patents

Description

Surface treated copper foil and laminated board using the same

The present invention relates to a surface-treated copper foil and a laminated board using the same, and more particularly to a surface-treated copper foil and a laminated board using the same, which is suitable for the transparency of a resin which requires a remaining portion of the copper foil to be etched.

In terms of the ease of wiring or the lightness, a small-sized electronic device such as a smart phone or a tablet PC uses a flexible printed wiring board (hereinafter referred to as FPC). In recent years, with the high functionality of these electronic devices, the speed of signal transmission has been increasing, and impedance matching has become an important factor in FPC. As a countermeasure against impedance matching in which the signal capacity is increased, thick layering of a resin insulating layer (for example, polyimide) which becomes an FPC substrate is progressing. Moreover, with the demand for higher density of wiring, the multi-layering of FPC has further developed. On the other hand, the FPC is subjected to processing such as bonding of a liquid crystal substrate or mounting of an IC wafer, and the alignment is performed by etching the copper foil in the laminate of the copper foil and the resin insulating layer. The positioning pattern recognized by the resin insulating layer is performed, and therefore, the visibility of the resin insulating layer becomes important.

Further, the copper clad laminate which is a laminate of the copper foil and the resin insulating layer can be produced by using a rolled copper foil having a roughened plating on its surface. The rolled copper foil is usually made of refined copper (oxygen content: 100 to 500 ppm by weight) or oxygen-free copper (oxygen content: 10 ppm by weight or less) as a raw material, and after hot rolling, the ingots are repeatedly subjected to cold rolling and Annealing is performed up to a predetermined thickness.

As such a technique, for example, Patent Document 1 discloses the following invention: The copper-clad laminate is obtained by laminating a polyimide film and a low-roughness copper foil, and the film after etching the copper foil has a light transmittance of 40% or more at a wavelength of 600 nm and a haze (HAZE) of 30% or less. Then the intensity is 500 N/m or more.

Further, Patent Document 2 discloses a flexible printed wiring board for COF having an insulating layer in which a conductor layer formed of an electrolytic copper foil is laminated, and the conductor layer is etched to form a circuit in an etching region. The light-transmitting property of the insulating layer is 50% or more, and the electrodeposited copper foil is provided with a rust-preventing layer using a nickel-zinc alloy on the surface next to the insulating layer, and the surface roughness (Rz) of the bonding surface is obtained. It is 0.05 to 1.5 μm, and the specular gloss at an incident angle of 60° is 250 or more.

Further, Patent Document 3 discloses a method for treating a copper foil for a printed circuit, which is a method for processing a copper foil for a printed circuit, characterized in that a surface of a copper foil is plated with a copper-cobalt-nickel alloy. After the roughening treatment, a cobalt-nickel alloy plating layer is formed to form a zinc-nickel alloy plating layer.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-98659

[Patent Document 2] WO2003/096776

[Patent Document 3] Japanese Patent No. 2849059

In Patent Document 1, the low-roughness copper foil obtained by the adhesion improving treatment by the organic treatment agent after the blackening treatment or the plating treatment may be used for the purpose of requiring flexibility for the copper-clad laminate. Broken due to fatigue, and there is a case where the resin has poor transparency.

Moreover, in Patent Document 2, the roughening treatment is not performed, and the flexible printed wiring board for COF is used. For the external use, the adhesion strength between the copper foil and the resin is low, but not sufficient.

Further, in the treatment method described in Patent Document 3, the copper foil may be subjected to fine treatment using Cu-Co-Ni. However, the resin obtained by removing the copper foil and the resin and removing the copper foil by etching cannot achieve excellent transparency.

The present invention provides a surface-treated copper foil excellent in transparency of a resin obtained by removing copper foil by etching, and a laminated board using the same.

As a result of intensive studies, the present inventors have found that the following conditions are not affected by the type of the substrate resin film or the thickness of the substrate resin film, and the resin transparency after etching the copper foil is affected: The surface-treated surface-treated copper foil is attached to the surface of the treated surface and the polyimide substrate is removed, and the printed matter with the mark is placed under it, and the printed matter is photographed by a CCD camera via a polyimide substrate. In the observation point-luminance graph obtained by the image of the marked portion, the slope of the luminance curve is controlled by focusing on the slope of the luminance curve near the end of the marked mark.

The present invention, which is completed on the basis of the above findings, is a surface-treated copper foil which is obtained by surface-treating at least one surface, and the surface of the copper foil adhered to the surface of the surface after treatment. After the two sides of the yttrium imide resin substrate are removed, the copper foil on both sides is removed by etching, and the printed matter printed with the linear mark is laid under the exposed polyimide substrate, and the CCD camera is used to sandwich the polyimide substrate. When the printed matter is photographed, the brightness of each observation point is measured in an image perpendicular to the direction in which the linear mark is observed in the image obtained by the photographing, thereby forming an observation point-luminance graph, and in the graph, The difference between the top average value Bt and the bottom average value Bb of the luminance curve generated from the end portion of the mark to the portion where the mark is not drawn is set to ΔB (ΔB=Bt-Bb), in the observation point-brightness chart, The value indicating the position of the intersection of the brightness curve and Bt closest to the intersection of the linear marks is set to t1, and the brightness curve is expressed in the range of 0.1 ΔB from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt. The value of the position closest to the intersection of the linear marks in the intersection of ΔB is t2. In this case, the Sv defined by the following formula (1) is 3.5 or more, and Sv=(ΔB×0.1)/(t1-t2 ) (1).

In one embodiment of the surface-treated copper foil of the present invention, the difference between the top average Bt and the bottom average Bb of the luminance curve generated from the end portion of the mark to the portion without the mark is ΔB (ΔB=Bt- Bb) is 40 or more.

In another embodiment of the surface-treated copper foil of the present invention, ΔB is 50 or more in the observation point-luminance chart produced based on the image obtained by the above-described photographing.

In still another embodiment of the surface-treated copper foil of the present invention, the Sv defined by the formula (1) in the luminance curve is 3.9 or more.

In still another embodiment of the surface-treated copper foil of the present invention, the Sv defined by the formula (1) in the luminance curve is 5.0 or more.

In still another embodiment of the surface-treated copper foil of the present invention, the surface treatment is a roughening treatment, and the average roughness Rz of the TD of the roughened surface is 0.30 to 0.80 μm, and the MD of the roughened surface is 60. The degree of gloss is 80 to 350%, and the ratio A/B of the surface area A of the roughened particles to the area B obtained by looking down the roughened particles from the surface side of the copper foil is 1.90 to 2.40.

In still another embodiment of the surface-treated copper foil of the present invention, the MD has a 60-degree gloss of 90 to 250%.

In still another embodiment of the surface-treated copper foil of the present invention, the TD is The average roughness Rz is from 0.35 to 0.60 μm.

In still another embodiment of the surface-treated copper foil of the present invention, the A/B is 2.00 to 2.20.

In still another embodiment of the surface treated copper foil of the present invention, the ratio of the 60 degree gloss of the MD of the roughened surface to the 60 degree gloss of TD is F (F = (60 degree gloss of MD) / ( The 60 degree gloss of TD)) is 0.80~1.40.

In still another embodiment of the surface treated copper foil of the present invention, the ratio of the 60 degree gloss of the MD of the roughened surface to the 60 degree gloss of TD is F (F = (60 degree gloss of MD) / ( The 60 degree gloss of TD)) is 0.90~1.35.

In still another embodiment of the surface-treated copper foil of the present invention, the surface root mean square height Rq of the surface-treated surface is 0.14 to 0.63 μm.

In still another embodiment of the surface-treated copper foil of the present invention, the surface of the surface-treated copper foil has a root mean square height Rq of 0.25 to 0.60 μm.

In still another embodiment of the surface-treated copper foil of the present invention, the surface of the surface-treated surface has a skewness Rsk of -0.35 to 0.53 based on JIS B0601-2001.

In still another embodiment of the surface-treated copper foil of the present invention, the surface has a skewness Rsk of -0.30 to 0.39.

In still another embodiment of the surface-treated copper foil of the present invention, the ratio E/G of the surface area G obtained by looking down the surface-treated surface to the convex portion volume E of the surface-treated surface is 2.11 to 23.91.

In still another embodiment of the surface-treated copper foil of the present invention, the ratio E/G is 2.95 to 21.42.

In still another embodiment of the surface-treated copper foil of the present invention, the ten-point average roughness Rz of the TD of the surface is 0.20 to 0.64 μm.

In still another embodiment of the surface-treated copper foil of the present invention, the ten-point average roughness Rz of the TD of the surface is 0.40 to 0.62 μm.

In still another embodiment of the surface-treated copper foil of the present invention, the ratio D/C of the three-dimensional surface area D of the surface to the two-dimensional surface area (surface area obtained when the surface is viewed) C is 1.0 to 1.7.

In another aspect, the present invention provides a laminate comprising a surface-treated copper foil of the present invention and a resin substrate.

In another aspect, the present invention is a printed wiring board using the surface treated copper foil of the present invention.

In another aspect, the invention is an electronic machine using the printed wiring board of the invention.

In still another aspect, the present invention provides a method of manufacturing a printed wiring board by connecting two or more printed wiring boards of the present invention to manufacture a printed wiring board to which two or more printed wiring boards are connected.

Still another aspect of the invention is a method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising the steps of: at least one printed wiring board of the invention, and another invention The printed wiring board or the printed wiring board which does not correspond to the printed wiring board of this invention is connected.

Still another aspect of the invention is an electronic device using one or more printed wiring boards to which at least one printed wiring board of the invention is connected.

Still another aspect of the invention is a method of manufacturing a printed wiring board comprising at least the step of connecting the printed wiring board of the present invention to a component.

According to still another aspect of the present invention, a method of manufacturing a printed wiring board having two or more printed wiring boards, comprising at least one of the printed wiring boards of the present invention and another invention The printed wiring board is not connected to the printed wiring board of the printed wiring board of the present invention; and the printed wiring board of the present invention or the printed wiring board to which the two or more printed wiring boards of the present invention are connected are connected to the component.

According to still another aspect of the invention, a printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating substrate, wherein the copper circuit is photographed by a CCD camera via the insulating resin substrate Observing the brightness of each observation point in an image obtained by the above-mentioned photographing in a direction perpendicular to the direction in which the copper circuit is observed to form an observation point-luminance graph, in which the end of the copper circuit is The top average value of the brightness curve generated by the portion to the portion without the copper circuit is set to Bt, the bottom average value is set to Bb, and the difference between the top average value Bt and the bottom average value Bb is obtained ΔB (ΔB=Bt- Bb), in the observation location-brightness graph, the value indicating the position of the intersection of the brightness curve and Bt closest to the copper circuit is set to t1, and the intersection of the self-luminance curve and Bt to 0.1 based on Bt The value in the ΔB depth range indicating the position of the intersection of the luminance curve and 0.1 ΔB closest to the intersection of the copper circuits is t2. In this case, the Sv defined by the following formula (1) is 3.5 or more, and Sv=(Δ B × 0.1) / (t1 - t2) (1).

According to still another aspect of the invention, a copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating substrate, wherein the copper foil of the copper-clad laminate is formed by etching After the linear copper foil, the CCD camera is used to pass through the above-mentioned insulating resin substrate. In the case of line photography, the brightness of each observation point is measured in the direction perpendicular to the direction in which the linear copper foil is observed in the image obtained by the above-mentioned photographing, and an observation point-brightness graph is formed in the graph. The top average value of the brightness curve generated from the end portion of the linear copper foil to the portion without the linear copper foil is Bt, the bottom average value is Bb, and the top average value Bt and the bottom average value Bb are obtained. Difference ΔB (ΔB=Bt-Bb), in the observation point-brightness chart, the value indicating the position of the intersection of the brightness curve and Bt closest to the above-mentioned linear surface-treated copper foil is set to t1, and will be The value of the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt indicates that the value of the position closest to the intersection of the linear surface-treated copper foil at the intersection of the brightness curve and 0.1 ΔB is t2, at this time, The Sv defined by the following formula (1) is 3.5 or more, and Sv = (ΔB × 0.1) / (t1 - t2) (1).

According to the present invention, it is possible to provide a surface-treated copper foil excellent in transparency of a resin obtained by removing copper foil by etching, and a laminate using the same.

Figure 1 is a schematic diagram defining Bt and Bb.

Figure 2 is a schematic diagram defining t1, t2, and Sv.

Fig. 3 is a schematic view showing a configuration of a photographing apparatus and a method of measuring a slope of a luminance curve when the slope of the luminance curve is evaluated.

Fig. 4a is a SEM observation photograph of the surface of the copper foil of Experimental Example B3-1 at the time of Rz evaluation.

Fig. 4b is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-1 at the time of Rz evaluation.

Fig. 4c is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-2 at the time of Rz evaluation.

Fig. 4d is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-3 at the time of Rz evaluation.

Fig. 4e is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-4 at the time of Rz evaluation.

Fig. 4f is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-5 at the time of Rz evaluation.

Fig. 4g is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-6 at the time of Rz evaluation.

Fig. 4h is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-7 at the time of Rz evaluation.

Fig. 4i is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-8 at the time of Rz evaluation.

Fig. 4j is a SEM observation photograph of the surface of the copper foil of Experimental Example A3-9 at the time of Rz evaluation.

Fig. 4k is a SEM observation photograph of the surface of the copper foil of Experimental Example B4-2 at the time of Rz evaluation.

Fig. 4 is a SEM observation photograph of the surface of the copper foil of Experimental Example B4-3 at the time of Rz evaluation.

Fig. 5 is a schematic view showing the surface morphology of the polyimide (PI) after copper foil etching in the case where the skewness Rsk of the surface of the copper foil is positive or negative.

[Formation and Manufacturing Method of Surface-treated Copper Foil]

The copper foil used in the present invention can be used as a copper foil which is produced by laminating a resin substrate and removing it by etching.

The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. In general, in order to increase the peeling strength of the copper foil on the surface of the resin substrate, that is, the surface of the surface-treated side, the surface of the copper foil after the degreasing may be subjected to roughening treatment of the surface of the copper foil after degreasing. . The electrolytic copper foil has irregularities at the time of production, and the convex portion of the electrolytic copper foil can be reinforced by the roughening treatment to further increase the unevenness. In the present invention, the roughening treatment is carried out by alloy plating such as copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating or nickel-zinc alloy plating. Further, it is preferably carried out by copper alloy plating. As the copper alloy plating bath, for example, a plating bath containing copper and one or more elements other than copper is preferably used, and it is more preferable to use copper and a material selected from the group consisting of cobalt, nickel, and arsenic. A plating bath of any one or more of the group consisting of tungsten, chromium, zinc, phosphorus, manganese, and molybdenum. Further, in the present invention, the roughening treatment is performed to increase the current density and shorten the roughening processing time as compared with the previous roughening treatment. There is a case where normal copper plating or the like is performed as a pre-roughening treatment, and in order to prevent the electrodeposited material from falling off, a normal copper plating or the like may be used as a refining treatment after roughening. The rolled copper foil and the electrolytic copper foil are also slightly different in handling.

Furthermore, the rolled copper foil of the present invention also includes a copper alloy foil containing one or more of elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V. . When the concentration of the above elements is increased (for example, 10% by mass or more in total), the electrical conductivity may be lowered. The electrical conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more. The total amount of the elements other than copper may be 0 mass% or more and 50 mass% or less, and may be 0.0001 mass% or more and 40 mass% or less, and may be 0.0005 mass% or more and 30 mass% or less, or may be 0.001 mass% or more. 20mass% or less.

The copper foil used in the present invention may be subjected to a roughening treatment or a roughening treatment to apply a heat-resistant plating layer (heat-resistant layer) or a rust-preventing layer (rust-proof layer) or a weather-resistant layer to the surface. As a treatment for applying a heat-resistant plating layer or a rust-preventive plating layer to the surface as the roughening treatment, a plating treatment of a Ni plating bath (1) or a Ni-Zn plating bath (2) under the following conditions can be used.

(Ni plating bath (1))

. Liquid composition: Ni20~30g/L

. pH: 2~3

. Current density: 6~7A/dm ²

. Bath temperature: 35~45°C

. Coulomb amount: 1.2~8.4As/dm ²

. Plating time: 0.2~1.2 seconds

(Ni-Zn plating bath (2))

. Liquid composition: nickel 20~30g/L, zinc 0.5~2.5g/L

. pH: 2~3

. Current density: 6~7A/dm ²

. Bath temperature: 35~45°C

. Coulomb amount: 1.2~8.4As/dm ²

. Plating time: 0.2~1.2 seconds

In addition, when the heat-resistant layer or the rust-preventive layer is provided on the copper foil by plating (normal plating instead of rough plating), the plating is necessary to be improved as compared with the prior art. Apply current density and shorten plating time.

In addition, the thickness of the copper foil used in the present invention is not particularly limited, and is, for example, 1 μm or more, 2 μm or more, 3 μm or more, or 5 μm or more, and is, for example, 3000 μm or less, 1500 μm or less, 800 μm or less, 300 μm or less, 150 μm or less, or 100 μm or less. 70 μm or less, 50 μm or less, and 40 μm or less.

Moreover, the manufacturing conditions of the electrolytic copper foil used in the invention of the present invention are shown below.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are those selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes

The copper-cobalt-nickel alloy plating as the roughening treatment can be formed by electroplating to form a nickel of -50 to 3000 μg/dm ² of cobalt -100 to 1500 μg/dm ² of nickel as an adhesion amount of 15 to 40 mg/dm ² . The ternary alloy layer is preferably formed by forming a ternary alloy layer such as copper-100-3000 μg/dm ² of cobalt-100-1500 μg/dm ² of nickel having an adhesion amount of 15 to 40 mg/dm ² . The way to implement. When the Co adhesion amount is less than 100 μg/dm ² , the heat resistance is deteriorated and the etching property is deteriorated. When the Co adhesion amount exceeds 3000 μg/dm ² , it is not preferable in the case where the influence of magnetism is necessary, and there is a case where an etching spot is generated and acid resistance and chemical resistance are deteriorated. If the Ni adhesion amount is less than 50 μg/dm ² , the heat resistance may be deteriorated. On the other hand, when the Ni adhesion amount exceeds 1500 μg/dm ² , there is a case where the etching residue increases. Preferably, the deposited mass of Co is 1000 ~ 2500μg / dm ^2, preferably of the deposited mass of nickel is 500 ~ 1200μg / dm ^2. Here, the etching spot refers to a case where Co is not dissolved and remains in the case of etching with copper chloride, and the etching residue refers to a case where Ni is not dissolved and remains in the case of performing alkali etching with ammonium chloride.

The plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating layer are as follows: plating bath composition: Cu 10~20g/L, Co 1~10g/L, Ni 1~10g/L

pH: 1~4

Temperature: 30~50°C

Current density D _k : 25~50A/dm ²

Plating time: 0.2~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. By roughening the film under the conditions of shortening the plating time and increasing the current density, the coarser particles which are finer than before are formed on the surface of the copper foil. Further, when the current density of the plating is set to be higher than the above range, the plating time must be set to be lower than the above range.

Further, the conditions for plating the copper-nickel-phosphorus alloy which is the roughening treatment of the present invention are shown below.

Composition of plating bath: Cu 10~50g/L, Ni 3~20g/L, P 1~10g/L

pH: 1~4

Temperature: 30~40°C

Current density D _k : 30~50A/dm ²

Plating time: 0.2~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. By roughening the film under the conditions of shortening the plating time and increasing the current density, the coarser particles which are finer than before are formed on the surface of the copper foil. Further, when the current density of the plating is set to be higher than the above range, the plating time must be set to be lower than the above range.

Further, the conditions of the copper-nickel-cobalt-tungsten alloy plating which is the roughening treatment of the present invention are shown below.

Composition of plating bath: Cu 5~20g/L, Ni 5~20g/L, Co 5~20g/L, W 1~10g/L

pH: 1~5

Temperature: 30~50°C

Current density D _k : 30~50A/dm ²

Plating time: 0.2~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. By roughening the film under the conditions of shortening the plating time and increasing the current density, the coarser particles which are finer than before are formed on the surface of the copper foil. Further, when the current density of the plating is set to be higher than the above range, the plating time must be set to be lower than the above range.

Further, the conditions of the copper-nickel-molybdenum-phosphorus plating alloy which is the roughening treatment of the present invention are shown below.

Composition of plating bath: Cu 5~20g/L, Ni 5~20g/L, Mo 1~10g/L, P 1~10g/L

pH: 1~5

Temperature: 30~50°C

Current density D _k : 30~50A/dm ²

Plating time: 0.2~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. By roughening the film under the conditions of shortening the plating time and increasing the current density, the coarser particles which are finer than before are formed on the surface of the copper foil. Further, when the current density of the plating is set to be higher than the above range, the plating time must be set to be lower than the above range.

After the roughening treatment, a cobalt-nickel alloy plating layer having a cobalt content of from 100 to 3000 μg/dm ^{2 to} 100 to 700 μg/dm ² of nickel may be formed on the roughened surface. This treatment can be regarded as a rust-proof treatment in a broad sense. The cobalt-nickel alloy plating layer must be formed to such an extent that the bonding strength between the copper foil and the substrate is not substantially lowered. When the cobalt adhesion amount is less than 200 μg/dm ² , the heat-resistant peel strength is lowered, and oxidation resistance and chemical resistance are deteriorated. Further, as another reason, if the amount of cobalt is small, the treated surface is easily reddish, which is not preferable. When the cobalt adhesion amount exceeds 3000 μg/dm ² , it is not preferable in the case where the influence of magnetism is necessary, and there is a case where an etching spot is generated, and acid resistance and chemical resistance are deteriorated. A preferred amount of cobalt adhesion is 500 to 2500 μg/dm ² . On the other hand, when the nickel adhesion amount is less than 100 μg/dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance are deteriorated. If the nickel exceeds 1300 μg/dm ² , the alkali etching property is deteriorated. A preferred nickel adhesion amount is 200 to 1200 μg/dm ² .

Moreover, the conditions for cobalt-nickel alloy plating are as follows: plating bath composition: Co 1~20g/L, Ni 1~20g/L

pH: 1.5~3.5

Temperature: 30~80°C

According to the present invention, a zinc plating layer having an adhesion amount of 30 to 250 μg/dm ² is further formed on the cobalt-nickel alloy plating layer. When the amount of zinc adhesion is less than 30 μg/dm ² , the effect of improving the heat-resistant deterioration rate may be lost. On the other hand, when the amount of zinc adhesion exceeds 250 μg/dm ² , the rate of deterioration of hydrochloric acid resistance may be extremely poor. The zinc adhesion amount is preferably from 30 to 240 μg/dm ² , more preferably from 80 to 220 μg/dm ² .

The conditions of the above zinc plating are as follows: plating bath composition: Zn 100~300g/L

pH: 3~4

Temperature: 50~60°C

Further, instead of the zinc plating layer, a zinc alloy plating layer such as a zinc-nickel alloy plating layer may be formed, and a rustproof layer may be formed by coating a chromate treatment or a decane coupling agent on the outermost surface.

The surface-treated copper foil of the present invention may be configured such that the surface treatment is roughening treatment, the average roughness Rz of the TD of the roughened surface is 0.30 to 0.80 μm, and the 60-degree gloss of the MD of the roughened surface is 80 to 350%, the ratio A/B of the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed from the surface side of the copper foil is 1.90 to 2.40. The surface roughness Rz(1), the glossiness (2), and the surface area ratio (3) of the particles of the copper foil having such a composition will be described below.

(1) Surface roughness Rz

The surface-treated copper foil having the above-described structure preferably has coarsened particles formed on the surface of the copper foil by roughening treatment, and the average roughness Rz of the TD of the roughened surface is 0.20 to 0.80 μm. With such a configuration, the peel strength is improved and the resin is well adhered to, and the tree after the copper foil is removed by etching. The transparency of the grease is improved. As a result, it is easier to perform alignment and the like at the time of mounting the IC wafer via the positioning pattern recognized by the resin. If the average roughness Rz of the TD is less than 0.20 μm, there is a fear of manufacturing cost for producing an ultra-smooth surface. On the other hand, when the average roughness Rz of the TD exceeds 0.80 μm, the unevenness of the surface of the resin after the removal of the copper foil by etching is increased, and as a result, there is a problem that the transparency of the resin is deteriorated. The average roughness Rz of the TD of the roughened surface is preferably from 0.30 to 0.70 μm, more preferably from 0.35 to 0.60 μm, still more preferably from 0.35 to 0.55 μm, still more preferably from 0.35 to 0.50 μm. Further, in the case where the surface-treated copper foil of the present invention is used in the use of the Rz, the average roughness Rz of the TD of the roughened surface of the surface-treated copper foil of the present invention is preferably 0.20 to 0.70 μm. The ratio is preferably 0.25 to 0.60 μm, more preferably 0.30 to 0.60 μm, still more preferably 0.30 to 0.55 μm, and still more preferably 0.30 to 0.50 μm.

In the case of the surface-treated copper foil of the present invention, the "roughening treatment surface" refers to a case where a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like after the roughening treatment. The surface of the surface treated copper foil after the surface treatment.

(2) Glossiness

The gloss of the incident angle of 60 degrees in the rolling direction (MD) of the surface of the surface-treated copper foil on the surface-treated side (for example, the roughened surface) greatly affects the transparency of the above resin. That is, the more the copper foil having a higher gloss on the surface (for example, the roughened surface) on the surface-treated side, the better the transparency of the resin. Therefore, the surface-treated copper foil having the above composition preferably has a gloss of 76 to 350%, preferably 80 to 350%, more preferably 90 to 300%, and even more preferably 90 to 250. %, and more preferably 100~250%.

Furthermore, by controlling the gloss of the MD of the copper foil before the surface treatment and the surface roughness of the TD Rz, which can control Sv and ΔB of the present invention. Further, by controlling the gloss of the TD of the copper foil before the surface treatment and the surface roughness Rz of the TD, the Sv, Rsk, Rq and the ratio E/G of the present invention can be respectively controlled.

Specifically, the surface roughness (Rz) of the TD of the copper foil before the surface treatment is 0.30 to 0.80 μm, preferably 0.30 to 0.50 μm, and the gloss at an incident angle of 60 degrees in the rolling direction (MD) is 350~ 800%, preferably 500 to 800%, and further, if the current density is increased and the roughening treatment time is shortened compared with the previous roughening treatment, the incident angle 60 of the rolling direction (MD) of the surface-treated copper foil after the surface treatment is performed. The gloss of the degree is 90~350%. Further, Sv and ΔB can be controlled to predetermined values. Such a copper foil can be produced by calendering (high gloss rolling) by adjusting the oil film equivalent of the rolling oil or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Thus, by setting the surface roughness (Rz) of the TD of the copper foil before the treatment and the gloss of the MD to the above range, the surface roughness (Rz) and surface area, Sv, Δ of the treated copper foil can be easily controlled. B. Further, in order to further reduce the surface roughness (Rz) of the surface-treated copper foil (for example, Rz = 0.20 μm), the roughness (Rz) of the TD of the treated side surface of the copper foil before the surface treatment is obtained. It is set to 0.18 to 0.80 μm, preferably 0.25 to 0.50 μm, and the gloss at an incident angle of 60 degrees in the rolling direction (MD) is 350 to 800%, preferably 500 to 800%, which is thicker than the previous one. The treatment increases the current density and shortens the roughening time.

Further, the copper foil before the roughening treatment is preferably a 60-degree gloss of MD of 500 to 800%, more preferably 501 to 800%, and still more preferably 510 to 750%. If the 60-degree gloss of the MD of the copper foil before the roughening treatment is less than 500%, the transparency of the above-mentioned resin becomes poor as compared with the case of 500% or more, and if it exceeds 800%, it may be produced. It is difficult to carry out the problem of manufacturing.

Further, the high gloss rolling can be carried out by setting the oil film equivalent of the following formula to 13,000 to 24,000 or less. Furthermore, it is intended to further reduce the surface roughness (Rz) of the surface treated copper foil (example) In the case of Rz = 0.20 μm, high gloss rolling is performed by setting the oil film equivalent of the following formula to 12,000 or more and 24,000 or less.

Oil film equivalent = {(calender oil viscosity [cSt] × (passing plate speed [mpm] + roll peripheral speed [mpm])} / {(roller meshing angle [rad]) × (material drop stress [kg/mm ² ])}

The rolling oil viscosity [cSt] is a dynamic viscosity of 40 °C.

Since the oil film equivalent is set to 13,000 to 24,000, a known method such as using a low-viscosity rolling oil or slowing the speed of the sheet can be used.

The chemical polishing system uses an etching solution such as a sulfuric acid-hydrogen peroxide-water system or an ammonia-hydrogen peroxide-water system, and the concentration is lowered as usual, and the etching is carried out for a long period of time.

Further, the above control method is also the same as the case where the heat-resistant layer or the rust-preventing layer is provided on the copper foil by plating (normal plating instead of plating of rough plating), and the roughening treatment is omitted.

The ratio of the 60 degree gloss of the MD of the treated surface such as the roughened surface to the 60 degree gloss of TD (F = (60 degree gloss of MD) / (60 degree gloss of TD)) is preferably 0.80~ 1.40. If the ratio F of the 60-degree gloss of the MD of the roughened surface to the 60-degree gloss of TD is less than 0.80, the transparency of the resin is lowered as compared with the case of 0.80 or more. Moreover, when the ratio F exceeds 1.40, the transparency of the resin is lowered as compared with the case of 1.40 or less. The ratio F is preferably from 0.90 to 1.35, and more preferably from 1.00 to 1.30.

(3) Surface area ratio of particles

The ratio A/B of the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed from the surface side of the copper foil greatly affects the transparency of the above resin. That is, when the surface roughness Rz is the same, the transparency of the resin is better as the copper foil having a smaller A/B ratio. Therefore, the surface-treated copper foil having the above configuration preferably has a ratio A/B of 1.90 to 2.40, more preferably 2.00 to 2.20.

By controlling the current density and the plating time at the time of particle formation, the morphology or formation density of the particles can be determined, and the surface roughness Rz, the glossiness, and the area ratio A/B of the particles can be controlled.

As described above, the ratio A/B of the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed from the surface side of the copper foil is controlled to 1.90 to 2.40, and the unevenness of the surface is increased, and the TD of the roughened surface is increased. The average roughness Rz is controlled to be 0.30 to 0.80 μm to remove the extremely thick portion of the surface, and on the other hand, the gloss of the roughened surface can be increased to 80 to 350%. By performing such control, the particle size of the roughened particles of the roughened surface in the surface-treated copper foil of the present invention can be reduced. The particle size of the roughened particles affects the transparency of the resin after etching and removing the copper foil. However, such control means that the particle size of the roughened particles is reduced within an appropriate range, and therefore, the transparency of the resin after etching and removing the copper foil is changed. It is better and the peel strength is also better.

As described above, the ratio A/B of the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed from the surface side of the copper foil is controlled to 1.90 to 2.40, and the unevenness of the surface is increased, and the TD of the roughened surface is increased. The average roughness Rz is controlled to be 0.30 to 0.80 μm to remove the extremely thick portion of the surface, and on the other hand, the gloss of the roughened surface can be increased to 80 to 350%. By performing such control, the particle size of the roughened particles of the roughened surface in the surface-treated copper foil of the present invention can be reduced. The particle size of the roughened particles affects the transparency of the resin after etching and removing the copper foil. However, such control means that the particle size of the roughened particles is reduced within an appropriate range, and therefore, the transparency of the resin after etching and removing the copper foil is changed. It is better and the peel strength is also better.

[copper foil surface root mean square height Rq]

The surface-treated copper foil of the present invention preferably has a root mean square height Rq of at least one surface of 0.14 to 0.63 μm. According to this configuration, the peel strength is improved and the resin is satisfactorily adhered to, and the transparency of the resin after the copper foil is removed by etching is improved. As a result, it is recognized by passing through the resin. It is easy to position the pattern and the like when mounting the IC wafer. When the root mean square height Rq is less than 0.14 μm, the roughening treatment of the surface of the copper foil may be insufficient, and the problem of insufficient adhesion to the resin may occur. On the other hand, when the root mean square height Rq exceeds 0.63 μm, the unevenness of the surface of the resin after the copper foil is removed by etching increases, and as a result, the transparency of the resin becomes poor. The surface root height Rq of the roughening treatment is more preferably 0.25 to 0.60 μm, and still more preferably 0.32 to 0.56 μm.

Here, the surface root mean square height Rq is an index indicating the degree of unevenness in the surface roughness measurement by the non-contact type roughness meter according to JIS B 0601 (2001), and is expressed by the following formula, and is the Z-axis of the surface roughness. The height of the unevenness (convex portion) of the direction is the root mean square of the height Z(x) of the convex portion in the reference length lr.

The root mean square height Rq of the height of the convex portion in the reference length lr: √ {(1/lr) × ∫ Z ² (x) dx (wherein integral is a cumulative value of 0 to lr)}

Further, when the surface treatment is not roughened, the plating film is treated at a low current density so that the plating film cannot be formed as described above, and when the roughening treatment is performed, by forming The high current density causes the roughened particles to be miniaturized, and plating is performed in a short time, whereby surface treatment with less roughness can be performed, thereby controlling the surface root mean square height Rq.

[The skewness of the copper foil surface Rsk]

The skewness Rsk represents the Z(x) cubic average of the reference length obtained by dimensionless calculation of the cube root mean square height Rq.

The root mean square height Rq is an index indicating the degree of unevenness in the surface roughness measurement by the non-contact type roughness meter according to JIS B 0601 (2001), and is expressed by the following formula (A), and is the Z-axis direction of the surface roughness. The height of the unevenness (protrusion) is the root mean square of the height Z(x) of the convex portion in the reference length lr.

The root mean square height Rq of the height of the convex portion in the reference length lr:

The skewness Rsk is expressed by the following formula (B) using the root mean square height Rq.

The skewness Rsk of the surface of the copper foil is an index indicating the objectivity of the unevenness on the surface of the copper foil when the average surface of the uneven surface of the copper foil is centered. As shown in FIG. 5, when Rsk<0, the height distribution is shifted to the upper side with respect to the average plane, and if Rsk>0, the height distribution is shifted to the lower side with respect to the average plane. When the deviation from the upper side is large, when the copper foil is attached to the polyimide and then removed by etching, the surface of the PI is concave. If the light is irradiated from the light source, the diffuse reflection inside the PI becomes large. . When the deviation from the lower side is large, when the copper foil is attached to the polyimide and then removed by etching, the surface of the PI is convex. If the light is irradiated from the light source, the diffuse reflection of the PI surface becomes large. .

The surface-treated copper foil of the present invention preferably controls the skewness Rsk of at least one surface to be -0.35 to 0.53. According to this configuration, the peel strength is improved and the resin is satisfactorily adhered to, and the transparency of the resin after the copper foil is removed by etching is improved. As a result, it is easy to perform alignment and the like at the time of mounting the IC wafer via the positioning pattern recognized by the resin. When the skewness Rsk is less than -0.35, surface treatment such as roughening treatment of the surface of the copper foil is insufficient, and the problem of insufficient adhesion to the resin cannot be obtained. On the other hand, when the skewness Rsk exceeds 0.53, the unevenness of the surface of the resin after removal of the copper foil by etching increases, and as a result, the transparency of the resin becomes poor. Table The skewness Rsk of the surface of the surface treated copper foil is preferably -0.30 or more, preferably -0.20 or more, preferably -0.10 or less. Further, the surface roughness of the copper foil surface is preferably 0.15 or more, preferably 0.20 or more, preferably 0.50 or less, preferably 0.45 or less, preferably 0.40 or less, and further preferably 0.39 or less. . Further, the skewness Rsk of the surface of the surface-treated copper foil is preferably -0.30 or more, preferably 0.50 or less, more preferably 0.39 or less.

Further, when the surface treatment is not roughened, the plating film is treated at a low current density so that the plating film cannot have irregularities as described above, and when the roughening treatment is performed, by forming The high current density causes the roughened particles to be miniaturized, and plating is performed in a short time, whereby surface treatment with less roughness can be performed, thereby controlling the skewness Rsk of the surface.

[The ratio of the surface area G of the copper foil surface to the volume E of the convex portion E/G]

The surface-treated copper foil of the present invention preferably has a ratio E/G of a surface area G obtained by observing the surface on at least one surface to a convex portion volume E of the surface of 2.11 to 23.91. According to this configuration, the peel strength is improved and the resin is satisfactorily adhered to, and the transparency of the resin after the copper foil is removed by etching is improved. As a result, it is easy to position and the like at the time of mounting the IC wafer via the positioning pattern recognized by the resin. When the ratio E/G is less than 2.11 μm, the roughening treatment of the surface of the copper foil is insufficient, and the problem of the resin may not be sufficiently caused. On the other hand, when the ratio E/G exceeds 23.91 μm, the unevenness of the surface of the resin after removal of the copper foil by etching increases, and as a result, the transparency of the resin becomes poor. It is preferably 2.95 to 21.42 μm, and more preferably 10.54 to 13.30 μm, more preferably than E/G.

Here, the "surface area G obtained when the surface is viewed from the surface" refers to the total of the surface area which becomes a convex portion based on a certain height (threshold value) or a portion which becomes a concave portion.

In addition, "the convex volume E of the surface" means that the convexity is convex based on a certain height (threshold value). The sum of the parts of the part or the part that becomes the part of the recess.

Further, the control of the ratio E/G of the surface area G of the surface to the volume E of the convex portion is performed by adjusting the current density of the roughened particles and the plating time as described above. When the plating treatment is performed at a high current density, smaller roughened particles are obtained, and when the plating treatment is performed at a low current density, large roughened particles are obtained. The number of particles formed under these conditions is determined according to the plating treatment time. Therefore, the convex portion volume E is determined according to the combination of the current density and the plating time.

[Average roughness Rz of copper foil surface]

The surface-treated copper foil of the present invention may be a roughened copper foil or a roughened copper foil formed with roughened particles. Preferably, the average roughness Rz of the roughened surface is 0.20 to 0.64 μm. . According to this configuration, the peel strength is further improved and the resin is satisfactorily adhered to, and the transparency of the resin after the copper foil is removed by etching is further improved. As a result, it is easier to position the IC wafer during mounting by the positioning pattern recognized by the resin. When the average roughness Rz of the TD is less than 0.20 μm, the roughening treatment of the surface of the copper foil may be insufficient, and there is a problem that the resin cannot be sufficiently adhered to the resin. On the other hand, when the average roughness Rz of the TD exceeds 0.64 μm, the unevenness of the surface of the resin after the removal of the copper foil by etching is increased, and as a result, there is a problem that the transparency of the resin is deteriorated. The average roughness Rz of the TD of the treated surface is preferably from 0.40 to 0.62 μm, more preferably from 0.46 to 0.55 μm.

In order to further improve the visibility of the present invention, the roughness (Rz) and gloss of the TD of the copper foil-treated side surface before the surface treatment are controlled. Specifically, the TD of the copper foil before the surface treatment (the direction perpendicular to the rolling direction (the width direction of the copper foil) is perpendicular to the direction of the foil passing through the copper foil in the electrolytic copper foil manufacturing apparatus for the electrolytic copper foil. The surface roughness (Rz) is 0.20 to 0.55 μm, preferably 020 to 0.42 μm. As such a copper foil, by adjusting The oil film equivalent of the calendering oil is calendered (high gloss calendering) or the surface roughness of the calendering roll is adjusted for calendering, or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Thus, by setting the surface roughness (Rz) of the TD of the copper foil before the treatment to the above range, the TD gloss of the copper foil before the treatment is set to the following range, and the surface roughness of the treated copper foil is controlled. Degree (Rz), surface area, Sv, Rq, Rsk, ratio of surface area G of the surface of the copper foil to the volume E of the convex portion E/G.

Further, in the copper foil before the surface treatment, the 60 degree gloss of TD is 400 to 710%, preferably 500 to 710%. If the 60-degree gloss of the MD of the copper foil before the surface treatment is less than 400%, the transparency of the above-mentioned resin becomes poor as compared with the case of 400% or more, and if it exceeds 710%, it is difficult to produce. The problem of manufacturing.

Further, the high gloss rolling can be carried out by setting the oil film equivalent specified by the following formula to 13,000 to 24,000 or less.

Oil film equivalent = {(calendering oil viscosity [cSt]) × (passing plate speed [mpm] + roll peripheral speed [mpm])} / {(roller meshing angle [rad]) × (material's lodging stress [kg/mm] ² ])}

The rolling oil viscosity [cSt] is a dynamic viscosity of 40 °C.

In order to set the oil film equivalent to 13,000 to 24,000, a known method such as using a low-viscosity rolling oil or slowing the speed of the sheet can be used.

The surface roughness of the calender roll can be, for example, 0.01 to 0.25 μm in terms of arithmetic mean roughness Ra (JIS B0601). When the value of the arithmetic mean roughness Ra of the calender roll is large, the roughness (Rz) of the surface of the copper foil before the surface treatment is increased, and the surface of the copper foil before the surface treatment is 60 degrees of the TD. The tendency to reduce gloss. Further, when the value of the arithmetic mean roughness Ra of the calender roll is small, the roughness (Rz) of the surface of the copper foil before the surface treatment is reduced, The tendency of the TD of 60 degree gloss of the surface of the copper foil before the surface treatment to be improved.

The chemical polishing system uses an etching solution such as a sulfuric acid-hydrogen peroxide-water system or an ammonia-hydrogen peroxide-water system, and the concentration is lowered as usual, and the etching is carried out for a long period of time.

[Slope of brightness curve]

After the surface-treated copper foil of the present invention is applied to both sides of the resin of the polyimide substrate, the copper foil on both sides is removed by etching, and the printed matter printed with the linear mark is laid under the exposed polyimide substrate. When the printed matter is photographed by the CCD camera through the polyimide substrate, the brightness of each observation point is measured in an image perpendicular to the direction in which the linear mark is observed to be observed. In the graph, the difference between the top average Bt and the bottom average Bb of the luminance curve generated from the end portion of the mark to the portion where the mark is not drawn is ΔB (ΔB=Bt-Bb). In the observation point-brightness chart, the intersection point indicating the closest to the above-mentioned linear mark in the intersection of the brightness curve and Bt is set to t1, and the brightness is expressed from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt. The intersection point of the curve closest to the above-mentioned linear mark in the intersection of the curve and 0.1 ΔB is t2, and at this time, the Sv defined by the formula (1) is 3.5 or more.

Sv=(△B×0.1)/(t1-t2) (1)

Further, in the above-described observation position-luminance graph, the horizontal axis represents position information (pixel × 0.1), and the vertical axis represents the value of luminance (gray scale).

Here, the "top average value Bt of the luminance curve", the "bottom average value Bb of the luminance curve", and the following "t1", "t2", and "Sv" will be described with reference to the drawings.

FIGS. 1(a) and 1(b) are schematic diagrams showing the definition of Bt and Bb when the width of the mark is set to about 0.3 mm. When the width of the mark is set to about 0.3 mm, there is a V-shaped brightness curve as shown in FIG. 1(a), and has a bottom as shown in FIG. 1(b). The case of the brightness curve. In either case, the "top average value Bt of the brightness curve" indicates the brightness at the time of measuring 5 points (the total of 10 parts on both sides) at intervals of 30 μm from the position of the end position on both sides of the distance mark at 50 μm. average value. On the other hand, the "base value Bb of the brightness curve" indicates the lowest value of the brightness of the front portion of the V-shaped concave portion when the brightness curve is V-shaped as shown in Fig. 1(a). (b) In the case of having a bottom, it means a value of a center portion of about 0.3 mm.

Fig. 2 is a schematic diagram showing definitions of t1, t2, and Sv. "t1 (pixel × 0.1)" indicates the value of the intersection of the brightness curve and Bt closest to the above-mentioned linear mark and the position of the intersection (the above-mentioned observation point - the value of the horizontal axis of the brightness chart). "t2 (pixel × 0.1)" is the intersection point from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt, and the intersection of the brightness curve and the 0.1 ΔB closest to the above-mentioned linear mark and the intersection point The value of the position (the above observation point - the value of the horizontal axis of the brightness chart). In this case, the slope of the luminance curve expressed by the line connecting t1 and t2 is calculated by Sv (gray scale/pixel × 0.1) in which the y-axis direction is 0.1 ΔB and the x-axis direction is (t1-t2). definition. Furthermore, one pixel on the horizontal axis corresponds to a length of 10 μm. Further, regarding Sv, both sides of the mark are measured and a small value is used. Further, when the shape of the luminance curve is unstable and there are a plurality of the above-mentioned "intersection points of the luminance curve and Bt", the intersection point closest to the mark is used.

In the above-described image captured by the CCD camera, the portion not marked with a high brightness is high, but the brightness is lowered just after reaching the end portion of the mark. When the visibility of the polyimide substrate is good, such a lowered state of brightness is clearly observed. On the other hand, if the recognition property of the polyimide substrate is poor, the brightness does not suddenly decrease from "high" to "low" in the vicinity of the mark end portion, but the state of the reduction is gentle, and the state of the brightness is not lowered. clear.

The present invention is based on the insight that the combination of the surface treated copper foil of the present invention is removed. The yttrium imide substrate is provided with a printed matter with a mark thereon, and an observation point-brightness chart is obtained from the image of the mark portion taken by the CCD camera via the polyimide substrate, and the mark end depicted in the chart The slope of the brightness curve near the part is controlled. More specifically, the difference between the top average value Bt of the luminance curve and the bottom average value Bb is set to ΔB (ΔB=Bt-Bb), and in the observation point-brightness graph, it will represent the intersection of the luminance curve and Bt. The value closest to the position of the intersection of the linear marks (the above-mentioned observation point - the value of the horizontal axis of the luminance chart) is set to t1, and is expressed from the intersection of the luminance curve and Bt to the depth of 0.1 ΔB based on Bt. The value of the position of the intersection of the brightness curve and the 0.1ΔB closest to the intersection of the linear marks (the value of the observation point-the horizontal axis of the brightness chart) is t2, and the Sv defined by the above formula (1) is 3.5 or more. According to this configuration, the recognition power of the mark sandwiched between the polyimides obtained by the CCD camera is improved without being affected by the type or thickness of the substrate resin. Therefore, it is possible to produce a polyimide substrate having excellent visibility, and when the polyimide substrate is subjected to predetermined treatment by an electronic substrate manufacturing step or the like, the positioning accuracy obtained by the marking is improved, thereby improving the yield, and the like. effect. Sv is preferably 3.9 or more, more preferably 4.5 or more, still more preferably 5.0 or more, and still more preferably 5.5 or more. The upper limit of Sv is not particularly limited, and is, for example, 70 or less, 30 or less, 15 or less, or 10 or less. According to this configuration, the boundary between the mark and the unmarked portion is more clear, the positioning accuracy is improved, the error caused by the mark image recognition is reduced, and the positional alignment can be performed more accurately.

[Area ratio of copper foil surface]

The ratio D/C of the three-dimensional surface area D of the surface on the surface of the copper foil to the two-dimensional surface area C greatly affects the transparency of the above resin. In other words, when the surface roughness Rz is the same, the transparency of the resin becomes better as the copper foil having a smaller D/C ratio. Therefore, the surface-treated copper foil of the present invention preferably has a ratio D/C of 1.0 to 1.7, more preferably 1.0 to 1.6. Here, the surface treatment side table When the ratio D/C of the three-dimensional surface area D of the surface to the two-dimensional surface area C is, for example, roughened, the surface area D of the roughened particles and the copper foil from the surface side of the copper foil are obtained. The ratio of area C is D/C.

The surface roughness of the surface treated copper foil or the morphology or formation density of the roughened particles is determined by controlling the current density and the plating time of the surface treatment during the surface treatment such as the formation of the roughened particles, and the surface roughness can be controlled. Rz, gloss and area ratio of the surface of the copper foil D/C, Sv, ΔB, Rq, Rsk, the ratio of the surface area G of the surface of the copper foil to the volume E of the convex portion E/G.

[etching factor]

In the case where the value of the etching factor when the copper foil is used to form the circuit is large, the tail of the circuit generated at the time of etching is reduced, so that the space between the circuits can be narrowed. Therefore, it is preferable that the value of the etching factor is large to form a circuit using a fine pattern. In the surface-treated copper foil of the present invention, for example, the value of the etching factor is preferably 1.8 or more, preferably 2.0 or more, preferably 2.2 or more, preferably 2.3 or more, and more preferably 2.4 or more.

Further, the printed wiring board or the copper clad laminate can measure the area ratio (A/B), gloss, surface roughness Rz, Sv of the above-mentioned particles for the surface of the copper circuit or the copper foil by melting and removing the resin. ΔB, Rq, Rsk, ratio E/G of the surface area G of the surface of the copper foil to the volume E of the convex portion.

[transmission loss]

In the case where the transmission loss is small, the attenuation of the signal at the time of signal transmission at a high frequency can be suppressed, so that the circuit transmitting at a high frequency can perform stable signal transmission. Therefore, it is preferable that the value of the transmission loss is small for a circuit use for transmitting a signal at a high frequency. After the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), the characteristic impedance was changed to 50 Ω by etching. In the microstrip line, the transmission coefficient is measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz is obtained. In this case, the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB/10 cm, more preferably. It is less than 4.1 dB/10 cm, and more preferably less than 3.7 dB/10 cm.

The surface-treated copper foil of the present invention can be bonded to the resin substrate from the surface of the surface-treated surface to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper substrate phenol resin, a paper substrate epoxy resin, or a synthetic fiber cloth substrate epoxy resin can be used for the rigid PWB. , glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., can be used for FPC polyester film or polyimide film, liquid crystal polymerization (LCP) film, Teflon (registered trademark) film, and the like.

In the case of the rigid PWB, the method of bonding is to impregnate the resin into a substrate such as a glass cloth to cure the resin to a semi-hardened prepreg. The copper foil can be superposed on the surface opposite to the coating layer and superposed on the prepreg, and heated and pressurized. In the case of FPC, a substrate such as a polyimide film may be laminated on a copper foil under high temperature and high pressure via an adhesive or without an adhesive, or the polyimide precursor may be coated. A laminate is produced by drying, hardening, or the like.

The thickness of the polyimide substrate resin is not particularly limited, and is usually 25 μm or 50 μm.

The laminate of the present invention can be used for various printed wiring boards (PWB), and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, it can be applied to one-sided PWB, two-sided PWB, and multi-layer PWB (three or more layers). From the viewpoint of the type of the insulating substrate material, it can be applied to rigid PWB, flexible PWB (FPC), and soft and hard composite PWB.

(Layering board and positioning method using the printed wiring board using the same)

A method of positioning a laminate of the surface-treated copper foil and the resin substrate of the present invention will be described. First, a laminate of a surface-treated copper foil and a resin substrate is prepared. Specific examples of the laminated sheet of the surface-treated copper foil and the resin substrate of the present invention include at least one of a main substrate, an attached circuit substrate, and a resin substrate such as a polyimide which is electrically connected thereto. In an electronic device including a flexible printed circuit board having a copper wiring formed thereon, a flexible printed circuit board is accurately positioned and pressure-bonded to the wiring board of the main board and the attached circuit board. In other words, in this case, the laminated board is a laminated body which is bonded by crimping the flexible printed circuit board to the wiring end portion of the main substrate, or by using the flexible printed circuit board and the circuit board. The laminated board in which the wiring end portions are crimped and bonded to each other. The laminate has indicia formed from a portion of the copper wiring or other material. The position of the mark is not particularly limited as long as it is a position at which the resin constituting the laminate can be imaged by a photographing means such as a CCD camera.

In the laminate thus prepared, when the mark is imaged by a photographing means via a resin, the position of the mark can be satisfactorily detected. Further, by detecting the position of the mark as described above, the position of the laminated sheet of the surface-treated copper foil and the resin substrate can be satisfactorily performed based on the position of the mark detected. Moreover, when a printed wiring board is used as a laminated board, the positioning means can be similarly detected by the positioning method, and the positioning of the printed wiring board can be performed more accurately.

Therefore, when a printed wiring board is connected to another printed wiring board, it is considered that the connection failure is reduced and the yield is improved. Further, as a method of connecting one printed wiring board to another printed wiring board, soldering or connection via an anisotropic conductive film (ACF) or via an anisotropic conductive paste (Anisotropic Conductive Paste) may be used. A known connection method such as connection of ACP) or connection via a conductive adhesive. Furthermore, in the present invention, the "printed wiring board" also includes a printed wiring board on which components are mounted, a printed circuit board, and a printed circuit. Brush the substrate. Further, two or more printed wiring boards of the present invention can be connected to each other to manufacture a printed wiring board to which two or more printed wiring boards are connected, and at least one printed wiring board of the present invention can be printed with another printed image of the present invention. The wiring board or the printed wiring board which does not correspond to the printed wiring board of this invention is connected, and the electronic device can also be manufactured using such a printed wiring board. Furthermore, in the present invention, the "copper circuit" also includes copper wiring. Further, the printed wiring board of the present invention can be connected to a component to manufacture a printed wiring board. Further, the connection of the present invention can be further achieved by connecting at least one printed wiring board of the present invention to another printed wiring board of the present invention or a printed wiring board which does not correspond to the printed wiring board of the present invention. A printed wiring board having two or more printed wiring boards is connected to the components, and a printed wiring board having two or more printed wiring boards connected thereto is manufactured. Here, examples of the "parts" include electronic components such as a connector, an LCD (Liquid Cristal Display), and a glass substrate used in an LCD, and include an IC (Integrated Circuit) and an LSI (Large scale). Electronic components such as integrated circuits, large integrated circuits, VLSI (Very Large Scale Integrated Circuit), ULSI (Ultra-Large Scale Integrated circuit), and other semiconductor integrated circuits (such as ICs) A wafer, an LSI wafer, a VLSI wafer, a ULSI wafer, a component for shielding an electronic circuit, and a component necessary for fixing a cover or the like to a printed wiring board.

Furthermore, the positioning method of the embodiment of the present invention may include a step of moving a laminate (including a laminate of a copper foil and a resin substrate or a printed wiring board). The moving step can be moved by, for example, a conveyor such as a belt conveyor or a chain conveyor, and can be moved by a moving device having an arm mechanism, and can be moved by floating the laminated plate by using a gas. Moving the device or moving the device, or moving the device or moving means (including rollers or bearings) by moving the laminated plate by rotating a substantially cylindrical shape or the like, and moving the oil pressure as a power source Device or moving means, moving device or moving means using air pressure as power source, moving device or moving means using motor as power source, linear guide stage with bracket moving, air guiding platform for bracket moving ( The air guide stage), the stacked linear guide platform, the linear motor drive platform and the like move the mobile device or the moving means. Further, the moving step can be performed by a known moving means.

Furthermore, the positioning method of the embodiment of the present invention can also be used in a surface mounter or a mounter.

Further, the laminated board of the surface-treated copper foil and the resin substrate positioned in the present invention may be a printed wiring board having a resin board and a circuit provided on the resin board. Moreover, in this case, the above-mentioned mark may be the above circuit.

In the present invention, "positioning" includes "detecting the position of a mark or object." Further, in the present invention, "positioning" includes "moving the marker or object to a predetermined position based on the detected position after detecting the position of the marker or the object".

Further, in the printed wiring board, instead of the mark of the printed matter, the circuit on the printed wiring board can be marked as a mark, and the circuit is photographed by a CCD camera via a resin, and the value of Sv is measured. Further, in the copper clad laminate, after the copper is formed into a line shape by etching, the linear copper is photographed by a CCD camera via a resin instead of the mark of the printed matter, using the linear copper as a mark. And determine the value of Sv.

Further, in the embodiment of the copper-clad laminate according to the present invention, the insulating resin substrate and the copper foil are formed, and the copper foil of the copper-clad laminate is formed into a linear copper foil by etching, and then the above-mentioned copper foil is interposed therebetween. When the insulating resin substrate is photographed by a CCD camera, the brightness of each observation point is measured in the direction perpendicular to the direction in which the linear copper foil is observed in the image obtained by the above-described photographing, thereby forming an observation point-luminance chart. In the chart, it will be from the above-mentioned linear copper foil The top average value of the brightness curve generated from the end portion to the portion without the above-mentioned linear copper foil is set to Bt, the bottom average value is set to Bb, and the difference between the top average value Bt and the bottom average value Bb is obtained ΔB (ΔB) =Bt-Bb), in the observation point-brightness chart, the value indicating the position of the intersection of the brightness curve and the Bt closest to the above-mentioned linear surface-treated copper foil is t1, and the intersection of the self-luminance curve and Bt The value in the depth range of 0.1 ΔB based on Bt indicates that the position of the intersection of the luminance curve and the 0.1 ΔB closest to the intersection of the linear surface-treated copper foil is t2, and the formula (1) is defined. Sv is 3.5 or more.

Further, the copper-clad laminate according to the present invention is an embodiment in which an insulating resin substrate and a surface-treated copper foil laminated on the surface side of the surface treatment and the insulating substrate are laminated, and the copper-clad coating is performed by etching. After the surface-treated copper foil of the laminated board is formed into a linear surface-treated copper foil, the image obtained by the above-mentioned photographing is photographed by the CCD camera through the insulating resin substrate laminated on the surface side of the surface treatment. The brightness of each observation point is measured in a direction perpendicular to the direction in which the linear surface-treated copper foil is observed to be observed, and an observation point-brightness chart is formed. In the figure, the end portion of the copper foil is treated from the above-mentioned linear surface. The top average value of the brightness curve generated by the portion to the above-mentioned linear surface-treated copper foil is set to Bt, the bottom average value is set to Bb, and the difference between the top average value Bt and the bottom average value Bb is obtained ΔB (ΔB) =Bt-Bb), in the observation point-brightness chart, the value indicating the position of the intersection of the brightness curve and the Bt closest to the above-mentioned linear surface-treated copper foil is set to t1, and the self-luminance curve and Bt are set. The value of the intersection point to the position of the 0.1 ΔB depth based on Bt indicates that the position of the intersection of the brightness curve and the 0.1 ΔB closest to the intersection of the linear surface-treated copper foil is t2, and the formula (1) is defined. The Sv is 3.5 or more.

When a printed wiring board is manufactured using such a copper-clad laminate, the printed wiring can be more accurately performed. The positioning of the board. Therefore, when one printed wiring board is connected to another printed wiring board, it is considered that the connection failure is reduced and the yield is improved.

[Examples]

<About Experimental Example A1-1~A1-30, Experimental Example B1-1~B1-14>

As Experimental Examples A1-1 to A1-30 and Experimental Examples B1-1 to B1-14, various copper foils described in Tables 2 and 3 were prepared, and one surface was subjected to roughening treatment under the conditions described in Table 1. Plating treatment.

After the above rough plating treatment, Experimental Examples A1-1~A1-10, A1-12~A1-27, Experimental Examples B1-3, B1-4, B1-6, B1-9~B1-14 The next plating treatment for forming the heat-resistant layer and the rust-preventing layer is performed. The formation conditions of the heat-resistant layer 1 are shown as follows.

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

Furthermore, the plating time is set to 0.5 to 2.0 seconds.

The heat-resistant layer 2 is formed on the copper foil to which the above heat-resistant layer 1 is applied. The formation conditions of the heat-resistant layer 2 are shown below.

Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

Further, in Experimental Examples B1-5, B1-7, and B1-8, the roughening plating treatment was not performed, and the heat-resistant layer 3 was directly formed on the prepared copper foil. The formation conditions of the heat-resistant layer 3 are shown as follows.

Liquid composition: nickel 25g / L, zinc 2g / L

pH: 2.5

Liquid temperature: 40 ° C

Current density: 6A/dm ²

Coulomb amount: 4.8As/dm ²

Plating time: 0.8 seconds

Further, in Experimental Example B1-15, the roughening plating treatment was not performed, and the heat-resistant layer 4 was directly formed on the prepared copper foil. The formation conditions of the heat-resistant layer 4 are shown as follows.

Liquid composition: nickel 0.3g / L, zinc 2.5g / L, pyrophosphate bath

Liquid temperature: 40 ° C

Current density: 5A/dm ²

Coulomb amount: 22.5As/dm ²

Plating time: 4.5 seconds

On the copper foil to which the heat-resistant layers 1 and 2 or the heat-resistant layer 3 or the heat-resistant layer 4 are applied, a rust-preventing layer is further formed. The formation conditions of the rustproof layer are shown below.

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0~2A/dm ² (for impregnation chromate treatment)

Coulomb amount: 0~2As/dm ² (for impregnation chromate treatment)

A weather-resistant layer is further formed on the copper foil to which the heat-resistant layers 1 and 2 and the rust-preventing layer are applied. The formation conditions are expressed as follows.

Using N-2-(aminoethyl)-3-aminopropyltrimethoxydecane as an amine-based decane coupling agent (Experimental Examples A1-17, A1-24~A1-27), N-2 -(Aminoethyl)-3-aminopropyltriethoxydecane (Experimental Example A1-1~A1-16), N-2-(Aminoethyl)-3-aminopropylmethyl Dimethoxydecane (Experimental Examples A1-18, A1-28, A1-29, A1-30), 3-aminopropyltrimethoxydecane (Experimental Example A1-19), 3-aminopropyltri Ethoxy decane (Experimental Examples A1-20, A1-21), 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine (Experimental Example 22), N- Phenyl-3-aminopropyltrimethoxydecane (Experimental Example A1-23) was applied and dried to form a weather resistant layer. Two or more of these decane coupling agents may be used in combination. Similarly, Experimental Examples B1-1 to B1-14 were coated and dried with N-2-(aminoethyl)-3-aminopropyltrimethoxydecane to form a weather resistant layer.

Further, the rolled copper foil was produced in the following manner. The copper ingots having the compositions shown in Tables 2 and 3 were subjected to hot rolling, and then subjected to annealing and cold rolling in a continuous annealing line at 300 to 800 ° C to obtain a rolled sheet having a thickness of 1 to 2 mm. The rolled sheet was annealed at 300 to 800 ° C for annealing and recrystallization, and finally cold rolled until the thickness of Table 2 to obtain a copper foil. The "fine copper" in the "Category" column of Tables 2 and 3 indicates the refined copper based on JIS H3100 C1100, and the "oxygen-free copper" indicates the oxygen-free copper based on JIS H3100 C1020. Further, "fine copper + Ag: 100 ppm" means that 100 mass ppm of Ag is added to the refined copper.

The electrolytic copper foil is an electrolytic copper foil HIP foil manufactured by JX Nippon Mining & Metal Co., Ltd. In the case of electrolytic polishing or chemical polishing, the thickness of the plate after electrolytic polishing or chemical polishing is described.

In addition, Table 2 and Table 3 describe the point of the copper foil production process before surface treatment. "High gloss rolling" means final cold rolling (cold rolling after final recrystallization annealing) at the value of the oil film equivalent described. "Normal calendering" means that the final cold rolling is performed at the value of the oil film equivalent described (the cold rolling after the final recrystallization annealing). "Chemical polishing" and "electrolytic polishing" are carried out under the following conditions.

In the "chemical polishing", H ₂ SO ₄ is 1 to 3% by mass, and H ₂ O ₂ is 0.05 to 0.15% by mass. The polishing time of the remaining portion of water is used to set the polishing time to 1 hour.

"Electrolytic polishing" is carried out under the conditions of a phosphoric acid 67% + sulfuric acid 10% + water 23% at a voltage of 10 V/cm ² and the time shown in Table 2 (if electrolytic polishing is performed for 10 seconds, the polishing amount becomes 1 to 2 μm. )get on.

<About Experimental Example A2-1~A2-7, B2-1~B2-2, A3-1~A3-9, B3-1~B3-5, A4-1~A4-8, B4-1~B4- 5>

In the experimental examples, each of the copper foils described in Tables 6, 8, and 10 was prepared, and one surface was subjected to a plating treatment as a surface treatment under the conditions described in Tables 7, 9, and 11. Also, those who have not been roughened are also prepared. "None" in the "Roughening" column of the "Surface Treatment" of the table indicates that the surface treatment is not roughening, and "Yes" indicates that the surface treatment is roughening.

Further, the rolled copper foil ("perfected copper" in the "Type" column of the table indicates rolled copper foil) was produced as follows. After the predetermined copper ingot is produced, after hot rolling, the continuous annealing line at 300 to 800 ° C is repeatedly subjected to annealing and cold rolling to obtain a rolled sheet of 1 to 2 mm thick. The rolled sheet was annealed at 300 to 800 ° C for annealing and recrystallization, and finally cold rolled until the thickness of Table 1 to obtain a copper foil. The "fine copper" in the table indicates fine copper based on JIS H3100 C1100.

Further, the table describes the main points of the copper foil production step before the surface treatment. "High gloss calendering" It means that the final cold rolling (cold rolling after the final recrystallization annealing) is carried out at the value of the oil film equivalent described. Further, in Experimental Examples A3-1, A3-2, A4-1, and A4-2, copper foils having copper foil thicknesses of 6 μm, 12 μm, and 35 μm were also produced and evaluated. As a result, it was the same as the case where the thickness of the copper foil was 18 μm.

Each of the samples of the examples and the comparative examples produced as described above was subjected to various evaluations in the following manner.

. Determination of surface roughness (Rz):

The surface-treated copper foil of each of the examples and the comparative examples was measured using a contact roughness meter Surfcorder SE-3C manufactured by Kosaka Research Co., Ltd., and a surface roughness of 10 points was measured according to JIS B0601-1994. . In the direction of the rolling direction or the direction perpendicular to the traveling direction of the electrolytic copper foil in the manufacturing apparatus of the electrolytic copper foil under the conditions of the measurement reference length of 0.8 mm, the evaluation length of 4 mm, the cutoff value of 0.25 mm, and the conveying speed of 0.1 mm/sec (TD) The measurement position was changed 10 times, and the value of 10 measurements was obtained.

Further, the surface roughness (Rz) of the copper foil before the surface treatment was also determined in the same manner.

In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

. Determination of surface root mean square height Rq:

The surface-treated surface of the copper foil after the surface treatment of each of the examples and the comparative examples was measured by the laser microscope OLS4000 manufactured by Olympus Corporation, and the root mean square height Rq of the copper foil was measured. Copper foil table When the magnification of the surface is 1000 times, the value of the rolled copper foil is measured by the measurement in the direction perpendicular to the rolling direction (TD) or the electrolytic copper foil is used under the condition that the evaluation length is 647 μm and the cutoff value is zero. The value was determined by measurement in the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the apparatus for manufacturing an electrolytic copper foil. Further, the measurement ambient temperature of the surface root mean square height Rq obtained by a laser microscope was set to 23 to 25 °C.

. Determination of the skewness of the surface Rsk:

The surface-treated surface of the copper foil after the surface treatment of each of the examples and the comparative examples was measured by the laser microscope OLS4000 manufactured by Olympus Corporation, and the skewness Rsk of the surface-treated surface of the copper foil was measured. When the magnification of the surface of the copper foil is 1000 times, the value of the rolled copper foil is determined by the measurement in the direction perpendicular to the rolling direction (TD), or for the electrolytic copper, under the condition that the evaluation length is 647 μm and the cutoff value is zero. The foil was obtained by measuring the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the apparatus for producing an electrolytic copper foil. Further, the measurement ambient temperature of the surface skewness Rsk obtained by the laser microscope was set to 23 to 25 °C.

. Determination of the ratio of the surface area G of the copper foil surface to the volume E of the convex portion E/G:

The surface-treated surface of the copper foil after the surface treatment of each of the examples and the comparative examples was measured by the laser microscope OLS4000 manufactured by Olympus Corporation, and the surface area G and the convex portion volume E obtained in plan view were measured to calculate the ratio E/G. The value was obtained on the condition that the evaluation area was 647 μm × 646 μm and the cutoff value was zero. Further, the measurement ambient temperature of the surface area G and the convex portion volume E obtained by the use of a laser microscope in a plan view was 23 to 25 °C.

. Area ratio (D/C):

With respect to the surface-treated surface of the copper foil after the surface treatment of each of the examples and the comparative examples, the surface area of the surface of the copper foil was measured by a laser microscope. The copper foil after the surface treatment of each of the examples and the comparative examples was a laser microscope OLS4000 manufactured by Olympus Co., Ltd., and the area of the treated surface was 20 times the equivalent of 647 μm × 646 μm (surface area obtained in plan view) C. The three-dimensional surface area D of (actual data: 417,953 μm ² ) was measured and calculated by the method of three-dimensional surface area D ÷ two-dimensional surface area C = area ratio (D/C). Further, the measurement ambient temperature of the three-dimensional surface area B obtained by a laser microscope was set to 23 to 25 °C.

. Area ratio of particles (A/B):

The surface area of the roughened particles is measured using a laser microscope. Using a laser microscope VK8500 manufactured by Ens Co., Ltd., the three-dimensional surface area A corresponding to an area B of 100 × 100 μm (actual data of 9982.52 μm ² ) in a magnification of 2000 times of the roughened surface was measured by the three-dimensional surface area A. The method of setting the two-dimensional surface area B = area ratio (A/B) is set. Further, the surface of the copper foil which was not subjected to the roughening treatment was also subjected to the measurement to calculate a three-dimensional surface area A ÷ two-dimensional surface area B = area ratio (A / B).

In addition, when the surface of the copper foil is roughened or not subjected to roughening treatment, and the surface treatment is performed in order to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like, the heat-resistant layer is subjected to rust prevention. The surface of the surface-treated copper foil after surface treatment such as a layer or a weather-resistant layer was subjected to the above measurement.

. Gloss:

A gloss meter Handy Gloss Meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z8741 is used in the rolling direction (MD, the direction of the foil in the case of electrolytic copper foil) and a direction perpendicular to the rolling direction ( In the case of TD or electrolytic copper foil, the incident angle is 60 degrees in the direction perpendicular to the direction of the foil, and the surface-treated surface (the roughened surface in the case where the surface treatment is roughened) is measured. Furthermore, after roughening the surface of the copper foil or not When the surface treatment is performed in order to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, or the like in the roughening treatment, the surface-treated copper foil subjected to surface treatment such as the heat-resistant layer, the rust-preventive layer, and the weather-resistant layer is used. The surface was subjected to the above measurement. Further, the copper foil before the surface treatment was also subjected to the gloss in the same manner.

. Slope of the brightness curve

The surface-treated copper foil was bonded to the polyimide film from the roughened surface side of the surface-treated copper foil (Experimental Examples A1-1 to A1-30, and Experimental Examples B1-1 to B1-14 were manufactured by Zhonghuan) Any of the polyimine films having a thickness of 25 μm or 50 μm or a thickness of 50 μm manufactured by Toray DuPont, Experimental Examples A2-1 to A2-7, B2-1 to B2-2, A3-1 to A3-9, and B3 -1~B3-5, A4-1~A4-8, B4-1~B4-5 are used on both sides of the PIXEO polyimine film with a thickness of 50 μm manufactured by Zhonghua and a double-layer copper-clad laminate. The copper foil was removed by etching (aqueous solution of ferric chloride) to prepare a sample film. In addition, when the surface of the copper foil is subjected to roughening treatment or is not subjected to roughening treatment, and the surface treatment is performed in order to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like, the heat-resistant layer is prevented. The surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer is bonded to both sides of the polyimide film from the surface of the surface-treated surface, and the surface-treated copper foil is removed by etching (aqueous solution of ferric chloride). Make a sample film. Then, the print with the printed black mark is laid under the sample film, and the printed matter is photographed by the CCD camera through the sample film, and the image obtained by the photograph is perpendicular to the direction in which the observed linear mark is extended. The direction was measured for the brightness of each observation point to prepare an observation point-luminance chart, in which the slope (angle) of the luminance curve generated from the end portion of the mark to the portion where the mark was not drawn was measured. A schematic diagram showing a method of measuring the configuration of the imaging device used at this time and the slope of the luminance curve is shown in FIG.

Further, ΔB and t1, t2, and Sv were measured by the following imaging apparatus as shown in Fig. 2 . again One pixel on the horizontal axis corresponds to a length of 10 μm.

The photographing apparatus includes a CCD camera, a platform (white) on which a polyimine substrate having a marked paper is placed, a light source for illuminating the photographing unit of the polyimide substrate, and a photographing unit attached to the lower side. The evaluation of the target paper was carried out by a conveyor on a platform (not shown) using a polyimide substrate. The main specifications of the photographic device are expressed as follows:

. Photographic device: sheet inspection device manufactured by Nireco Co., Ltd. Mujiken

. CCD camera: 8192 pixels (160MHz), 1024 grayscale digits (10 bits)

. Lighting power supply: high-frequency lighting power supply (power supply unit × 2)

. Lighting: Fluorescent (30W)

Furthermore, regarding the brightness shown in FIG. 3, 0 means "black", brightness 255 means "white", and the degree of gray between black and white (white and black, grayscale) is divided into 256 Displayed in grayscale.

. Identification (resin transparency):

The surface of the surface-treated copper foil on the surface of the surface-treated side was bonded to a polyimide film (Experimental Examples A1-1 to A1-30, and Experimental Examples B1-1 to B1-14 were made of a thickness of 25 μm or 50 μm. Or any of the polyimine films of thickness 50 μm manufactured by Toray DuPont, Experimental Examples A2-1~A2-7, B2-1~B2-2, A3-1~A3-9, B3-1~B3 -5, A4-1~A4-8, B4-1~B4-5 are etched (trichloro) using both sides of a 50 μm thick layer made of Zhonghua and a PIXEO polyimine film for a double-layer copper-clad laminate. The molten iron solution) removes the copper foil to form a sample film. In addition, when the surface of the copper foil is subjected to roughening treatment or is not subjected to roughening treatment, and the surface treatment is performed in order to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like, the heat-resistant layer is prevented. The surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer is bonded to both sides of the polyimide film from the surface of the surface-treated surface, and is etched (water-soluble by ferric chloride) Liquid) The surface treated copper foil is removed to form a sample film. A printed matter (black circle having a diameter of 6 cm) was attached to one surface of the obtained resin layer, and the visibility of the printed matter was judged from the opposite surface via the resin layer. When the length of the black circle of the printed matter is more than 90% of the circumference, it is judged as "◎", and the outline of the black circle is 80% or more of the circumference and the length of less than 90% is clearly defined as "○". (The above is acceptable), and the black circle contour is evaluated as "X" (failed) in the case where the length of the circle is 0 or more and the length is less than 80%.

. Peel strength (follow strength):

According to IPC-TM-650, the normal peeling strength is measured by the tensile tester autostereograph 100, and the normal peel strength of 0.7 N/mm or more is used as a laminate substrate. In addition, in the measurement of the peeling strength, Experimental Examples A1-1 to A1-30 and Experimental Examples B1-1 to B1-14 were used in the thickness of 25 μm or 50 μm manufactured by Zhonghua, or 50 μm in thickness manufactured by Toray Dupont. Any of the polyimide membranes, Experimental Examples A2-1 to A2-7, B2-1 to B2-2, A3-1 to A3-9, B3-1 to B3-5, A4-1 to A4-8, B4-1~B4-5 is a PIXEO polyimine film made of a 50 μm thick, double-layer copper-clad laminate produced by Zhonghua, and the polyimide film and the examples and comparative examples of the present invention are used. A surface-treated copper foil surface-treated surface is bonded to a sample. Further, in the measurement, the polyimide film is attached to a hard substrate (a stainless steel plate or a synthetic resin plate (not deformed in the peel strength measurement) by using a double-sided tape, or by using an instant The adhesive is attached and fixed. Further, the unit of the value of the peel strength in the table is N/mm.

. Solder heat resistance evaluation:

The surface of the surface-treated copper foil on the surface of the surface-treated side was bonded to the polyimide film (Experimental Examples A1-1 to A1-30, and Experimental Examples B1-1 to B1-14 were made by using a thickness of 25 μm or 50 μm, or any of the thicknesses of 50 μm made by Toray Dupont, experimental examples A2-1~A2-7, B2-1~B2-2, A3-1~A3-9, B3-1~ B3-5, A4-1~A4-8, and B4-1~B4-5 are both sides of a 50 μm thick manufactured by Zhonghua and a PIXEO polyimine film for a double-layer copper-clad laminate. The obtained two-area laminate was made into an attached test piece in accordance with JIS C6471. The prepared test piece was exposed to high temperature and high humidity of 85 ° C and 85% RH for 48 hours, and then floated in a solder bath of 300 ° C to evaluate the heat resistance of the solder. After the solder heat resistance test, in the interface between the copper foil roughening surface and the polyimide back surface of the polyimide film, the area of 5% or more of the area of the copper foil in the attached test piece was expanded to cause the interface discoloration to be evaluated as × (Failed), the case where the expansion discoloration area was less than 5% was evaluated as ○, and the case where the expansion discoloration did not occur at all was evaluated as ◎. In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was subjected to the above measurement.

. Yield

The surface of the surface-treated copper foil on the surface of the surface-treated side was bonded to a polyimide film (Experimental Examples A1-1 to A1-30, and Experimental Examples B1-1 to B1-14 were made of a thickness of 25 μm or 50 μm. Or any of the polyimine films of thickness 50 μm manufactured by Toray DuPont, Experimental Examples A2-1~A2-7, B2-1~B2-2, A3-1~A3-9, B3-1~B3 -5, A4-1~A4-8, B4-1~B4-5 are etched on both sides of the PIXEO polyimine film with a thickness of 50 μm and a double-layer copper-clad laminate. (Aqueous ferric chloride solution) was made into an FPC having a circuit width of L/S of 30 μm/30 μm. Thereafter, it was attempted to detect a mark of 20 μm × 20 μm square by a CCD camera via polyimide. The case where 9 or more times can be detected in 10 times is set to "◎", and the case where 7 to 8 times can be detected is set to "○", and 6 times can be detected. In the case of "△", the case where 5 or less times can be detected is set to "X". In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was subjected to the above measurement.

(10) Circuit shape obtained by etching (fine pattern characteristics)

The copper foil was bonded to both sides of a polyimide film (50 μm thick, Upilex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination. In order to evaluate the fine pattern circuit formability, it is necessary to make the thickness of the copper foil the same, here based on the thickness of the 12 μm copper foil. That is, when the thickness is thicker than 12 μm, the thickness is reduced to 12 μm by electrolytic polishing. On the other hand, when the thickness is thinner than 12 μm, it is thickened to a thickness of 12 μm by a copper plating treatment. The single-sided side of the two-layered laminate obtained is printed on the shiny side of the copper foil of the laminated board by a photosensitive resist coating and exposure step, and the unnecessary portion of the copper foil is etched by the following conditions. A fine pattern circuit such as L/S = 20/20 μm is formed. Here, the circuit width is such that the bottom width of the circuit section becomes 20 μm.

(etching conditions)

Device: spray type small etching device

Spray pressure: 0.2MPa

Etching solution: aqueous solution of ferric chloride (specific gravity 40 Baume)

Liquid temperature: 50 ° C

After the fine pattern circuit was formed, the photosensitive resist film was peeled off by immersing in an aqueous NaOH solution at 45 ° C for 1 minute.

. Calculation of the etching factor (Ef)

Using the scanning electron microscope photograph S4700 manufactured by Hitachi Global Advanced Technology Co., Ltd., the fine pattern circuit sample obtained above was observed from the upper portion of the circuit at a magnification of 2000 times, and the top width (Wa) of the upper portion of the circuit and the bottom width of the bottom portion of the circuit were measured. (Wb). The copper foil thickness (T) was set to 12 μm. The etching factor (Ef) was calculated by the following formula.

Etch factor (Ef)=(2×T)/(Wb-Wa)

In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was subjected to the above measurement.

. Measurement of transmission loss

In each sample, the surface of the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Chung-Chung Co., Ltd.), and the characteristic impedance was 50 Ω by etching. A microstrip line was formed, and the transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained. Further, in order to make the evaluation conditions as uniform as possible, after the surface-treated copper foil and the liquid crystal polymer resin were bonded together, the thickness of the copper foil was set to 18 μm. That is, when the thickness of the copper foil was thicker than 18 μm, the thickness was reduced to 18 μm by electrolytic polishing. On the other hand, in the case where the thickness is thinner than 18 μm, the thickness is increased to 18 μm by a copper plating treatment. As an evaluation of the transmission loss at a frequency of 20 GHz, 3.7 dB/10 cm is set to ◎, 3.7 dB/10 cm or more and less than 4.1 dB/10 cm is set to ○, and 4.1 dB/10 cm or more and less than 5.0 dB/ 10 cm is set to Δ, and 5.0 dB/10 cm or more is set to ×.

Furthermore, the printed wiring board or the copper clad laminate can be melted and removed by the resin, and the copper electric The above measurements were carried out on the road or copper foil surface.

In addition, when the surface of the copper foil is roughened or not subjected to roughening treatment, and the surface treatment is performed in order to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like, the heat-resistant layer is subjected to rust prevention. The surface of the surface-treated copper foil after surface treatment such as a layer or a weather-resistant layer was subjected to the above measurement.

The conditions and evaluations of the above tests are shown in Tables 1 to 11.

In the experimental example in which Sv satisfies the scope of the invention of the present invention, the recognition is good and the yield is good.

4 shows the experimental examples B3-1, (b) Experimental Example A3-1, (c) Experimental Example A3-2, (d) Experimental Example A3-3, and (e) Experimental Example at the time of Rz evaluation. A3-4, (f) Experimental Example A3-5, (g) Experimental Example A3-6, (h) Experimental Example A3-7, (i) Experimental Example A3-8, (j) Experimental Example A3-9, ( k) Experimental Example B3-2, (l) SEM observation photograph of the surface of the copper foil of Experimental Example B3-3.

Claims (28)

A surface-treated copper foil obtained by surface-treating at least one surface, and bonding the copper foil from the surface side of the surface treatment to both sides of the polyimide resin substrate, and removing the copper foil on both sides by etching a printed matter printed with a linear mark is laid under the exposed polyimide substrate, and when the printed matter is photographed by a CCD camera through the polyimide substrate, the image obtained by the photographing is followed by Observing the brightness of each observation point in the direction perpendicular to the direction in which the linear mark extends is made to form an observation point-brightness chart, in which the brightness curve generated from the end of the mark to the portion where the mark is not drawn is formed. The difference between the top average Bt and the bottom average Bb is set to ΔB (ΔB=Bt-Bb), and in the observation point-brightness graph, the intersection point of the brightness curve and Bt closest to the linear mark will be indicated. The value of the position is set to t1, and the value from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt represents the value of the position closest to the intersection of the linear mark in the intersection of the brightness curve and 0.1 ΔB. Set to t2, this In the case, the Sv defined by the following formula (1) is 3.5 or more, and Sv = (ΔB × 0.1) / (t1 - t2) (1). The surface-treated copper foil of claim 1, wherein a difference between a top average value Bt and a bottom average value Bb of a luminance curve generated from an end portion of the mark to a portion without the mark is ΔB (ΔB=Bt -Bb) is 40 or more. The surface-treated copper foil according to the second aspect of the invention, wherein the ΔB is 50 or more in the observation point-luminance chart produced from the image obtained by the photographing. The surface-treated copper foil according to claim 1, wherein the Sv defined by the formula (1) in the luminance curve is 3.9 or more. The surface-treated copper foil according to claim 4, wherein the Sv defined by the formula (1) in the luminance curve is 5.0 or more. The surface-treated copper foil according to claim 1, wherein the surface treatment is roughening, and the MD of the roughened surface has a 60-degree gloss of 76 to 350%, and the surface area A of the roughened particles is self-treated. The ratio A/B of the area B obtained when the surface of the copper foil is viewed from the surface of the roughened particles is 1.90 to 2.40. The surface treated copper foil of claim 6, wherein the MD has a 60 degree gloss of 90 to 250%. The surface treated copper foil of claim 6 wherein the A/B is 2.00 to 2.20. The surface treated copper foil according to claim 6 of the patent application, wherein the ratio of the 60 degree gloss of the MD of the roughened surface to the 60 degree gloss of the TD is F (F = (60 degree gloss of MD) / (TD) The 60 degree gloss)) is 0.80~1.40. The surface treated copper foil according to claim 9 of the patent application, wherein the ratio of the 60 degree gloss of the MD of the roughened surface to the 60 degree gloss of the TD is F (F = (60 degree gloss of MD) / (TD) The 60 degree gloss)) is 0.90~1.35. The surface-treated copper foil according to claim 1, wherein the surface of the surface-treated surface has a root mean square height Rq of 0.14 to 0.63 μm. The surface-treated copper foil according to claim 11, wherein the surface-treated copper foil has a root mean square height Rq of 0.25 to 0.60 μm. The surface-treated copper foil according to claim 11, wherein the surface of the surface-treated surface has a skewness Rsk of -0.35 to 0.53 based on JIS B0601-2001. The surface treated copper foil of claim 13, wherein the surface skewness Rsk is -0.30~0.39. The surface-treated copper foil of claim 1, wherein the ratio of the surface area G obtained by looking up the surface-treated surface to the convex portion volume E of the surface-treated surface E/G (μm) is 2.11~ 23.91. The surface treated copper foil of claim 15 wherein the ratio E/G (μm) is 2.95 to 21.42. The surface-treated copper foil according to claim 1, wherein a ratio D/C of the three-dimensional surface area D of the surface to the two-dimensional surface area (surface area obtained when the surface is viewed) C is 1.0 to 1.7. The surface treated copper foil of claim 17, wherein the D/C is 1.0 to 1.6. A laminated board comprising a surface-treated copper foil according to the first aspect of the patent application and a resin substrate. A printed wiring board using the surface-treated copper foil of the first application of the patent scope. An electronic machine using the printed wiring board of claim 20 of the patent application. A method of manufacturing a printed wiring board by connecting two or more printed wiring boards of claim 20 to manufacture a printed wiring board in which two or more printed wiring boards are connected. A method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising at least one of the steps of: at least one printed wiring board of claim 20, and another application patent item 20 The printed wiring board is not equivalent to the printed wiring board connection of the printed wiring board of claim 20 of the patent application. An electronic device using one or more printed wiring boards to which at least one printed wiring board of claim 22 or 23 is connected. A method of manufacturing a printed wiring board, which comprises at least printing of claim 20 The steps to connect the patch panel to the part. A method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising at least one step of printing at least one printed wiring board of claim 20 and printing of another application patent item 20 The wiring board is not equivalent to the printed wiring board connection of the printed wiring board of claim 20; and the printed wiring board of claim 20 or the connection of the patent application range 23 has two or more printed wirings The printed wiring board of the board is connected to the parts. A printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating substrate, and when the copper circuit is photographed by a CCD camera via the insulating resin substrate, an image obtained by the photographing is obtained Observing the brightness of each observation point in a direction perpendicular to the direction in which the copper circuit is observed to form an observation point-brightness graph, in which the portion from the end of the copper circuit to the portion without the copper circuit is generated The top average value of the brightness curve is set to Bt, the bottom average value is set to Bb, and the difference ΔB (ΔB=Bt-Bb) between the top average value Bt and the bottom average value Bb is obtained, in the observation place-brightness chart. , the value indicating the position of the intersection of the brightness curve and Bt closest to the copper circuit is set to t1, and the brightness curve is expressed in the range of 0.1 ΔB from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt. The value of the position closest to the intersection of the copper circuit in the intersection of ΔB is t2. In this case, the Sv defined by the following formula (1) is 3.5 or more, and Sv=(ΔB×0.1)/(t1-t2) (1). A copper clad laminate having an insulating resin substrate and a copper foil disposed on the insulating substrate When the copper foil of the copper clad laminate is formed into a linear copper foil by etching, and the image is taken by the CCD camera through the insulating resin substrate, the image obtained by the photographing is observed along the The brightness of each observation point is measured by the direction in which the linear copper foil extends in a direction perpendicular to the observation point-brightness graph, and in the graph, the end portion of the linear copper foil is removed from the end portion of the linear copper foil. The top average value of the generated brightness curve is set to Bt, the bottom average value is set to Bb, and the difference between the top average value Bt and the bottom average value Bb is obtained ΔB (ΔB=Bt-Bb) at the observation point-brightness In the graph, the value indicating the position of the intersection of the brightness curve and Bt closest to the linear surface-treated copper foil is set to t1, and the intersection of the self-luminance curve and Bt to the depth range of 0.1 ΔB based on Bt. The value indicating the position of the intersection of the luminance curve and the 0.1 ΔB closest to the linear surface-treated copper foil is t2. In this case, the Sv defined by the following formula (1) is 3.5 or more, and Sv=(Δ B × 0.1) / (t1 - t2) (1).